Monomers for flame resistant resinous copolymers



2,891,985 Patented June 23, 1959 United States t Patent "ice MONOMERSFOR FLAME RESISTANT RESINOUS 'COPOLYMERS Everett C. Hurdis, Clifton,John F. Petras, Glen Rock,

and Hendrik Romeyn, Jr., Montelair, N.J., assignors 'to United StatesRubber Company, New York, N.Y., a corporation of New Jersey 500 m1. oftoluene and 250 ml. of benzene. Ethyl phosphorodichloridate, 81.5 g. /2mol), was then added through the dropping funnelwhile nitrogen wasbubbled 5 in. Hydrogen chloride was'evolved at a moderate rate and wasdisposed of through a simple scrubber. The solvent was then graduallydistilled off, while'a slow stream of nitrogen was bubbled through themixture, over the course of three hours, the pot temperature rising toNo Drawing Application November 16, 1956 1 115 Additional solvent wasthen slowly distilled serial No. 22 519 ofi unhtill pot tlempereliltugereacled 45 C. and hydrogen c on e evo ution a cease otal reaction time 2260461) for this phase of the preparation was 7 hours.

The reaction mixture was again diluted by adding 450 This inventionrelates to novel symmetrical mixed new 1 ml. of toluene; then 148.5 g..(1 mol).of trans-betatral esters represented by the general formula(methoxycarbonyl) acrylyl chloride was added while the 0 C1 Cl 0 O3-0aPM...CHH a O Omofiuaacacaaaom] 01 (SH, 01

where R is an alkyl group containing from 1 to 4 carbon mixture refluxedactively at a pot temperature of 112 atoms.

C. The reaction was completed by refluxing with gradual These esters,like the unsaturated polyesters described takeofl of solvent over thecourse of six hours to a final in the Carleton Ellis U.S. Patent No.2,195,362, dated pot temperature of 145 C. Residual sol-vent was thenMarch 26, 1940, and U.S. Patent No. 2,255,313, dated 25 removed bydistillation under -40 mm. (water pump) September 9, 1941, can cop lym din C inat vacuum up to a maximum pot temperature of 150 C., with variousreactive (copolymerizable) ethylenic mono- The product was a glassysemi-solid at room temperature. mers, such as vinyltoluene, vinylacetate, Z-methyl-S-vinyl- That reaction had o curred t f th i d neutralpyridine, methyl methacrylate, diallyl phthalate, triallyl ester wasindicated by the following analysis:

cyanurate, N-vinylphthalimide, diallyl benzenephos- 30 phonate, etc., toprovide new and useful plastics. How-' ever, in contradistinction to theconventional unsaturated polyesters covered by the above mentioned Ellispatents,

. Calculated Observed the new monomers of this. invention have theimportant Acid m 0 50 y Hydroxyl Number. 0 17 advantage of formingcopolymers with a h1 gh degree of percent 2 226 flame resistance. Flameresistance in the hquid copoly- Phosphorus, p r nt 2, 274

merizable mixtures ,used for casting and laminating applications is aproperty much desired by'the trade.

7 1 Calculated for the following structure:

The special advantage of the new copolymerizable monomers of thisinvention lies in the fact that their intrinsic flame resistance is sohigh that copolymers containing as much as of an inflammable monomer,e.g., styrene, will still be self-extinguishing.

A further specific advantage of the new monomers of this invention istheir good resistance to discoloration on long exposure to light. Flameresistant copolymerizable mixtures based on polyesters containing eithertetrachlorophthalic acid or hexachloro-endomethylene-tetrahydrophthalicacid are available. However, these mixtures when polymerized have poorresistance to discoloration on light aging, while the copolymerizablemonomers of this invention give copolymers of superior light agingresistance.

As regards this invention, the advantages of flame resistance and lightaging resistance are achieved without sacrificing other physicalproperties as compared to general purpose polymerizablepolyester-styrene mixtures.

The following example is given to illustrate preparation and use of theesters, parts being by weight:

. The above symmetrical mixed neutral ester from 2 4:5 mols of 2,2-[isopropylidenebis(2,6-dichloro-p-phenyleneoxy) ldiethanol esterifiedwith 2 mols of methyl hydrogen fumarate and then with 1 mol of ethylphosphorodichloridate, as above, was copolymerized with styrene and withmixtures of styrene and diallyl benzene phosphonate. The products wereclear, hard, yellow plastics with useful properties. Evaluation data arelisted in Table I. It will be noted that physical properties are as goodas those obtained from commercial general-purpose un- 55 saturatedpolyester-styrene mixtures, While the additional advantage of high flameresistance is shown. Castings were self-extinguishing if styrene contentdid not exceed 40%.

The new monomer of this invention forms styrene copolymers withexcellent resistance to discoloration from light exposure. This wasshown by ultraviolet light aging of castings in comparison with twocommercial flame resistant copolymerizable mixtures with the samepercent EXAMPLE 1 of styrene. One of the commercial copolymers was basedA reactor equipped with dropping funnel, gas inlet t b on atetrachlorophthalic polyester, while the other commechanical stirrer,short fractionating column, and dismercial copolymer was based onhexachloro-endomethylt llation head Was charged with 454 8- 11ml) ofene-tetrahydrophthalic polyester. Copolymers from the[isopropylidenebis(zl'dchloro P phenyleneoxyn'dl' new monomer of thisexample showed less discoloration,

t was first $351231 33 2e$eit l1 1 O 315 the s ll even without lightstabilizer, than the commercial mateamount of water in the system beingremoved azeotropirials showed in the presence of light stabilizer.

cally. The pot temperature was then lowered by adding 2,891,985 p 3 4 7Table I mechanical stirrer, gas inlet tube and reflux condenser wascharged with: PROPERTIES OF OOPOLYMERSIsopropyl1deneb1s(2,6-d1chlorophenol), 2 mols g 732 Composition:Propylene glycol, used as solvent ml 150 Mixed neutral ester monomer,Benzyltrlmethylammonlum chloride, 60% aqueparts by weight 60 50 60 50 I.1 32 Styrene, parts by Weight- 40 50 30 40 0118 so 1011 Diallyl benzenephosphoflate, 50% sodiumhydroxide solutlon g 16 parts by weight 10 Y g988552; $6;, i 4 4 4 The charge was melted and kept at 105-115 C. whileat 0, 10 ethylene oxide was bubbled in. When the mixture had Pro erties:

IfiockwmRHardneSS 128 gained 170 grams in welght (theory 176 g.), thereac Tensile Strength, n nn n. 5, 392 tlon was discontinued. Thereaction mixture was then Elongation 1 at Brea ercen Young,S Modulusmsixlw) dissolved in 8 liters of hot methanol, and 4 l1ters of F Waterwere added to precipitate the product in crystalllne 268 288 238 gigform. By filtering and drying, 1398 g. of material melt- 310 300 8.2 14ing at 112 C.-114 C. was obtained. By adding an C 3:3 additional 2liters of water to the mother liquor a second 6%;gi z t g pg gg ,2g 9393 70 71 fraction weighting 191 g. of M.P. 109 C.112 C. was2.1bf,%m.$tfi ...ff3 0.26 0.25 i l r l yi l 1 T3; f ll win naly i urnlnt in. per min. y con me at t e pro uct was isopropyi ene is 2 .4 2 ZTest D6354) S e 0 8 S e S e (2,6-d1chloro-p-phenyleneoxy) Jd1ethanol.No'rE.Elongations were determined from jaw separations and Analysls:therefrire are} 1116) true absolitetvtilkugsi lls lor example, afjagsepiirizgion elonga ion 0 eorrespon s 0 eonga ion 0 a 0n gs lfi tmg ifimg 0 Calculated Observed In Example 1, the ethyl phosphorodichloridate(the ggggg fgffg g; 32% name adopted in Chemical Abstracts Index in1952) was Chlorine, percent 31.3 30.9

previously called ethoxyphosphoryl dichloride.

The trans-beta-(methoxycarbonyl)acrylyl chloride can Having thusdescribed our invention, what we claim also be called the methylhalf-ester half-chloride of and desire to protect by Letters Patent is:

fumaric acid. 1. A compound represented by the general formula 0 01 OH,01 0 0 R-O-i" -o-oH,orI,-o d--o on,on, -ofiiion=on-iiro0H,

01 (J a CI 2 The 2,2'- [isopropylidenebis(2,o-dichloro-p-phenylenewhereR is an alkyl group containing from 1 to 4 carbon oxy)]diethanol used inExample 1 is the subject of the atoms.

Hurdis and Petras application Serial No. 622,548, filed 2. A compoundrepresented by the formula 0 01 CH3 01 o o rhino-i-o-C:H,0-d--ocnL-oii-oH=OH-i J o0H,

01 :11 01 a concurrently herewith, and assigned also to the presentReferences Cited in the file of this patent 3353156,iiffiiicilfiiiiilniififilsi itigi UNITED STATES PATENTS 614,235).2,331,265 Coleman et al Oct. 5, 1943 A reaction flask of 2 litercapacity, equipped with 2557091 Gamrath at June 1951 2,631,168 Ross etal Mar. 10, 1953

1. A COMPOUND REPRESENTED BY THE GENERL FORMULA